Patent GB-876495-A (GB)
Title: New hydrophilic alkali and amine salts of carboxyl-group containing co-polymers and manufacture and application thereof
IPC: A61K8/81
Filed: 1957-12-30
Abstract: Alkali and amine salts of carboxyl-group-containing copolymers, which are soluble in polyhalogenated hydrocarbons that are gaseous at ordinary temperature and/or a mixture thereof with a water-soluble aliphatic alcohol containing 1-3 carbon atoms, may be prepared by processes wherein an ester, that can be hydrolysed in the polymerized condition, of a copolymerizable-ethylenically unsaturated carboxylic acid and an aliphatic alcohol containing 1-6 carbon atoms, is copolymerized, dissolved in a water-soluble solvent, together with an acrylamide of formula: <FORM:0876495/IV (a)/1> where R is hydrogen, methyl or ethyl, R1 is hydrogen or a monovalent hydrocarbon radical and R2 is a monovalent hydrocarbon radical (provided that when R1 is hydrogen the substituent R2 is attached to the amide nitrogen atom by means of a secondary or tertiary carbon atom), optionally with one or more copolymerizable compounds, and subsequently such a proportion of the ester groups are hydrolysed that the polymer salt becomes hydrophilic.  Many suitable esters, amides, copolymerizable compounds, water-soluble solvents and catalysts are listed and examples describe the copolymerization of (1) N-tertiary butyl acrylamide and ethyl acrylate in ethyl alcohol in the presence of benzoyl peroxide, followed by hydrolysis with potassium hydroxide and ethanol; (2 and 11) N-tertiary butyl acrylamide and ethyl acrylate; (3 and 4) N-tertiary butyl acrylamide, ethyl acrylate and methyl methacrylate; (5) N-diisobutyl acrylamide and methyl acrylate; (6) N-isopropyl acrylamide and ethyl acrylate; N-cyclohexyl acrylamide and (7) ethyl acrylate and (9) dimethyl itaconate; (8) N-isobornyl acrylamide and n-butyl acrylate; (10) N- cyclohexyl acrylamide and diethyl maleate; and (12) N-tertiary amyl acrylamide and dimethyl fumarate in isopropanol in the presence of benzoyl peroxide; (13) N-phenyl acrylamide and n-butyl acrylate in isopropanol; (14) N-diphenyl acrylamide and ethyl acrylate in methylene chloride; and (15) N-tertiary butyl methacrylamide and ethylacrylate in isopropanol in the presence of benzoyl peroxide and azodiisobutyronitrile; followed by hydrolysis with potassium hydroxide and isopropanol. Alcoholic solutions of the products may be used as hair fixatives, to which conventional ingredients such as lanolin, perfumes, dyes, silicone oils and waxes may be added.  These preparations may be mixed with halogenated hydrocarbon propellants, e.g. trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoroethane, for use in aerosol dispensers.ALSO:Hair fixative compositions comprise solutions in alcohols of alkali and amine salts of carboxyl group containing polymers prepared by copolymerizing in a water-soluble solvent esters of aliphatic alcohols containing 1 to 6 carbon atoms and ethylenically unsaturated carboxylic acids with acrylamides of the formula <FORM:0876495/VI/1> where is hydrogen, methyl or ethyl, R1 is hydrogen or a monovalent hydrocarbon radical and R2 is a monovalent hydrocarbon radical provided that when R1 is hydrogen the substituent R2 is attached to the amide nitrogen atom by a secondary or tertiary carbon atom, optionally with one or more copolymerizable compounds, and subsequently hydrolysing such a proportion of the ester groups that the polymer salt becomes hydrophilic (see Group IV (a)).  The compositions may also comprise lanolin, silicone oils and waxes, perfumes and dyes, and may be mixed with halogenated hydrocarbon propellants, e.g. trichlorofluoromethane, dichlorodifluoromethane and dichlorotetrafluoroethane, for use in aerosol dispensers. Examples describe fixative compositions comprising hydrolysed copolymers derived from (1 and 2) ethyl acrylate and N-tertiary butyl acrylamide with perfume oils and lanolin; (3) ethyl acrylate, methyl methacrylate and N-tertiary butyl acrylamide with (4) perfume oils and silicone oil; (5) methyl acrylate and N-diisobutyl acrylamide; (6) ethyl acrylate and N-isopropyl acrylamide; (7) ethyl acrylate and N-cyclohexyl acrylamide; (8) n-butyl acrylate and N-isobornyl acrylamide; (9) dimethyl itaconate and N-cyclohexyl acrylamide; (10) diethyl maleate and N-cyclohexyl acrylamide; (11) ethyl acrylate and N-tertiary amyl acrylamide; (12) dimethyl fumarate and N-tertiary amyl acrylamide; (13) n-butyl acrylate and N-phenyl acrylamide; (14) ethyl acrylate and N-diphenyl acrylamide; and (15) ethyl acrylate and N-tertiary butyl methacrylamide dissolved in ethanol, isopropanol or mixtures thereof, together with propellants.